CN102834550A - Anodic oxidation device - Google Patents
Anodic oxidation device Download PDFInfo
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- CN102834550A CN102834550A CN2011800182678A CN201180018267A CN102834550A CN 102834550 A CN102834550 A CN 102834550A CN 2011800182678 A CN2011800182678 A CN 2011800182678A CN 201180018267 A CN201180018267 A CN 201180018267A CN 102834550 A CN102834550 A CN 102834550A
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- power supply
- ribbon
- anodic oxidation
- supply drum
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/005—Apparatus specially adapted for electrolytic conversion coating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
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Abstract
In order to form at high speed an anodic oxidation film as an insulating layer on one side of a metal substrate, an anodic oxidation device is configured to comprise: a power supply drum (2) that supports through close contact a band-shaped material (1) made from an anodic oxidizable metal or a band-shaped material (1) having at least one surface made from a compound conductive metal foil, which is an anodic oxidizable metal, and a part (2a) where at least the band-shaped material (1) is adhered is made from a conductive material; an opposing electrode (3) disposed facing the power supply drum (2); an electrolysis tank (5) filled with an electrolyte (4) in which the opposing electrode and part of the power supply drum (2) that supports the band-shaped material (1) are immersed; a protective member (6) that is made from a non-conductive material that overlaps the end part in the width direction of the band-shaped material (1), which is closely supported by the power supply drum (2), and the part of the power supply drum to which the band-shaped material (1) is not adhered, thereby protecting these parts from the electrolyte (4); and a drive unit that is synchronized with the circumferential speed of the power supply drum (2), and which forces the protective member (6) and the band-shaped material (1), which is in close contact with the power supply drum (2), to travel together in the electrolyte (4).
Description
Technical field
The present invention relates to be suitable for being manufactured on substrate that use, that be used for semiconductor element in the semiconductor device such as solar cell, thin-film transistor circuit and indicating meter (image display device) and be used for the anodic oxidation device of the electrode of electrolytic condenser.
Background technology
From in light weight and viewpoint flexibility, compare with the thin-film solar cells that adopts glass substrate, use and adopt the thin-film solar cells of metal substrate to have bigger possibility.And, because metal substrate can withstand high temperatures be handled,, improve the light transfer characteristic of solar cell thus so there is solar cell more efficiently in expectation.
The module efficiency of solar module is improved through on same substrate, be connected in series solar battery cell and integrated these solar battery cells.At this moment, essential is on the metal substrate of solar module, to form insulation layer, and on this insulation layer, be provided for carrying out the semiconductor circuit layer of opto-electronic conversion.For example; Under adopting such as the situation of stainless steel series material as substrate; Essential is, through utilizing the gas phase process such as CVD or substrate is coated with the Si oxide compound to the liquid phase process such as sol-gel process or al oxide forms insulation layer.Yet, if form insulation layer, in insulation layer, generate aperture and crack probably, thereby have practical problems (patent documentation 1) aspect the large-area thin dielectric film stably making to have with these methods.
Simultaneously, adopting under the situation of aluminium as substrate, can obtain to have the insulating coating (patent documentation 2) that favourable tight contact performance does not have aperture through the anode oxide film that forms AAO.Yet, be known that if AAO is heated to 120 ° more than the C, generate crack (non-patent literature 1) among the AAO on aluminium, thereby cause the insulation characterisitic deterioration, particularly the problem of earial drainage electric current increase.In addition, aluminium deliquescing when about 200 ° of C, the integrity that has reached the above aluminium of this temperature thus is extremely little.In this aluminium, occur tension set (viscous deformation) probably, thereby when utilizing this aluminum manufacturing semiconductor device, it is essential that the strictness of relevant operation limits such as creep strain and buckling deformation.This causes that aluminium base is applied to outdoor solar cell and becomes difficult.
In order to solve foregoing problems, a kind of like this method has been proposed, that is, this method is used for AAO is formed on the substrate that is formed by so-called aluminium coating material as insulation layer, and then on the AAO layer, forms extinction composite semiconductor layer or electrode layer.In the method, can these layers be designed to make that the difference of thermal expansivity of thermal expansivity and composite semiconductor layer of metal substrate is less.Therefore, even during the step that forms the composite semiconductor layer (it is being carried out under 500 ° of high temperature more than the C), problem can not occur such as insulation layer breaks and the composite semiconductor layer is peeled off yet.In addition, compare, have higher specific tenacity and the hot strength of Geng Gao with aluminium bonded metal base with aluminium, and the operation during therefore being easy to make.
Not only need when adopting AAO, under high-voltage, can not lose efficacy by the insulation function of AAO as the insulation layer of battery module, and need be when applying voltage amount of leakage current less.That is, the AAO insulation layer need have high volume resistance.If amount of leakage current is bigger, the then current generated leakage current that will become between each battery, thus the generating efficiency of module is with deterioration.Therefore, the thickness of AAO need be for more than the 1 μ m, and is preferably more than the 5 μ m, to guarantee aforementioned properties.
Be used for continuously that the common apparatus of anodic oxidation aluminium strip has such structure, wherein, will supply power roller or power supply groove are placed on before the electrolyzer, to supply with electric current to aluminium.This electric current also flow to electrolyzer from power pack through aluminium.Anodic oxidation is electrolytic oxidation (under the situation of aluminium, being three electron reactions), and the thickness of AAO is proportional with the amount of the electric current through aluminium that flows.Therefore, must supply with and the proportional electric current of LV (line speed) (speed that aluminium strip moves).At this moment, in proportion electric current flow to electrolyzer from power pack through aluminium.Therefore, if AAO is thick more and LV is big more, then voltage decline becomes bigger and produces power loss.And, exist because of the IR heating causes the aluminium between power pack and the electrolyzer to produce the possibility of fusing, thereby have the upper limit to AAO thickness and LV.Heating and fusing restriction electric current are confirmed according to the resistance of aluminium strip per unit sectional area.Therefore, along with aluminium foil becomes thin more, the feasible AAO thickness and the upper limit of LV will become littler.
Simultaneously, there is the demand that only on a surface of the thin aluminium foil of band shape, forms thick AAO layer.An example of this application is aforementioned metal substrate with insulation layer.In this case, can mask be engaged to a surface and can utilize aforementioned means to make the AAO layer.Yet, have the upper limit to AAO thickness and LV.In addition, AAO cuts down type (substractive) overlay film, and it is different from additional classes (additive) overlay film that forms such as through plating.Therefore, under the situation of the edge entering of mask, form overlay film at electrolytic solution easily.Therefore, must select to have the mask of high adhesion characteristics.And; Under the situation of the belt metal foil (like coating material) that engages dissimilar metals; Must the mask adhesively attached to be bonded to the side edge surfaces that exposes dissimilar metals,, prevent the side reaction that causes because of the local element effect so that make them aspect electrochemistry, become inert.
The various devices of AAO film have been proposed to be used for only on one of them surface of aluminium strip, forming.Typical example is that the supporting drum with rounded section is placed in the anodizing tank, aluminium foil and drum is placed in intimate contact, and only with one of them surperficial anodic oxidation (patent documentation 3) of aluminium foil.In addition, the method (patent documentation 4) that a kind of wherein supporting drum has conductive characteristic and this supporting drum is powered has also been proposed.Under one situation of back, can directly supply power from the back surface of aluminium foil, can aforesaid voltage decline and heating be suppressed to negligible level thus.
Yet, in these technology, solution leakage takes place between supporting drum and aluminium foil easily.AAO is formed on the side towards anodizing tank of aluminium foil, makes the superpotential of this side become big.Therefore, if solution leakage is to supporting in the drum, then the direct current rheology between supporting drum and the opposite electrode is big, thereby causes with respect to the current loss that forms electric current towards the AAO overlay film of anodizing tank one side.In addition, this current loss has electrochemical action on the surface of rousing with aluminium foil closely contacts that supplies power.Therefore, have following possibility: anode oxide film will be formed on the aluminium of a side that closely contacts with the drum of supplying power; If power supply drum is formed by metal, then will become anodic oxidation or stand anode dissolution of the surface of power supply drum, thus cause contact resistance to increase and the local defect of generation such as spark at tight surface in contact place.
In order to solve foregoing problems, patent documentation 4 has proposed a kind of like this device, that is: the material of power supply drum is the so-called valve metal such as tantalum and niobium.Yet, in this device, be accompanied by electrolysis procedure, on the surface of valve metal, will generate the anodic oxidation overlay film.Therefore, contact resistance will increase gradually, thereby essential usually the replacing should the power supply drum.Yet this material is expensive, and frequent change is unpractical.Simultaneously, patent documentation 5 has proposed a kind of being used for and has prevented that through the tight surface in contact supplied water between aluminium foil and support roll electrochemical action from appearing at the technology at this tight surface in contact place.In addition, patent documentation 6 discloses a kind of like this structure, that is: two edges with aluminium foil cover with non-conductive compression belt under tension force, to prevent that electrolyte flow is in surface in contact.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-339081 communique
Patent documentation 2: TOHKEMY 2000-49372 communique
Patent documentation 3: japanese kokai publication hei 4-371892 communique
Patent documentation 4: japanese kokai publication sho 60-210931 communique
Patent documentation 5: japanese kokai publication hei 6-108289 communique
Patent documentation 6: japanese kokai publication sho 46-39441 communique
Non-patent literature
Non-patent literature 1: Mao Dao people such as (Kayashima), the 3 (2000), 21st page of the upright industrial technology institute in Tokyo RR
Summary of the invention
The problem that invention will solve
Yet the device of patent documentation 5 is not only complicated, and electrolytic solution can must be kept the concentration of electrolytic solution thus consistently by the water dilution on the tight surface in contact.In addition, if the thin water layer on the surface in contact produces gas because of electrolysis, then this film will become gaseous film, thereby increase contact resistance.As a result, there is the possibility that adopts this device will cause producing spark.Simultaneously, the disclosed method that is used under tension force, covering the edge of aluminium foil in patent documentation 6, these belts and power supply drum and aluminium foil sliding contact consistently by belt.Therefore, the position of these belts is departed from the edge of aluminium foil probably, thereby is difficult to carry out successive anodic oxidation operation.In addition, under the thin situation of aluminium foil, can produce gauffer, thereby exist electrolytic solution partly to flow to the possibility in the space between aluminium foil and the drum through gauffer because of the tension force that under pressure, applies.
As stated, aforesaid method all can not prevent to form the anodic oxidation overlay film in tight surface in contact one side fully.Therefore, can not solve the contact resistance problem of unstable.
The present invention develops in view of afore-mentioned.The purpose of this invention is to provide a kind of can be with at a high speed at the thin metal matrix plate or have the anodic oxidation device that forms anode oxide film on the same surface of high-resistance metal substrate.
The means of dealing with problems
Anodic oxidation device of the present invention is characterised in that and comprises: the power supply drum; The mode with tight contact of being used for this power supply drum support by can anodised metal ribbon or by at least one surface, have can anodised metal the ribbon processed of composite conducting tinsel, the constituting by electro-conductive material with the part that said ribbon closely contacts at least of said power supply drum; Be arranged to opposite electrode in the face of said power supply drum; Electrolyzer, this electrolyzer is filled with electrolytic solution, and what said opposite electrode and said power supply were roused supports in this electrolytic solution of part immersion of said ribbon with the tight mode that contacts; The guard block that forms by non-conducting material; The part that does not closely contact with said ribbon of the lateral ends of the said ribbon that said guard block imbrication is supported with the mode of tight contact by said power supply drum and said power supply drum is with said end and the bulging influence that does not receive said electrolytic solution with those parts that said ribbon closely contacts of said power supply of protecting said ribbon; And driving part, this driving part makes said guard block and the said ribbon that closely contact with said power supply drum move in said electrolytic solution with the mode with the synchronization of said power supply drum.
Preferably, in said power supply drum, recess is set, said ribbon contacts said recess and in said recess, moves.
Said anodic oxidation device can also comprise: guide reel, this guide reel are used for said guard block is expressed to said power supply drum.
Preferably, a plurality of holes are set in said opposite electrode.
Preferably; Stating the distance between power supply drum and the said opposite electrode by the part of the said electrolytic solution of entering of the said ribbon of said power supply drum supporting and/or the part place of leaving said electrolytic solution of said ribbon, stating the distance between power supply drum and the said opposite electrode greater than middle body place at the said electrolytic solution of immersion of said ribbon.
Preferably, said guard block is non-conductive rubber or the tinsel that covered by non-conductive rubber.
Preferably, the electro-conductive material of said power supply drum is conductive plastics or conductive rubber.
Preferably, the electromotive force of said opposite electrode is a negative polarity with respect to ground.
Preferably, the electromotive force of said ribbon is identical with earth potential, and the output of electrolysis power is insulated with respect to ground.
Preferably, said anodic oxidation device also comprises: supervision portion, this supervision portion are used to keep watch on the voltage with respect to earth potential of said power supply drum.
Continuous anodic oxidation device of the present invention is characterised in that and comprises: the anodic oxidation device a plurality of of the present invention of arranged in series.
The invention effect
Anodic oxidation device of the present invention comprises: the power supply drum; The mode with tight contact of being used for this power supply drum support by can anodised metal ribbon or by at least one surface, have can anodised metal the ribbon processed of composite conducting tinsel, the constituting by electro-conductive material with the part that said ribbon closely contacts at least of said power supply drum; Be arranged to opposite electrode in the face of said power supply drum; Electrolyzer, this electrolyzer is filled with electrolytic solution, and what said opposite electrode and said power supply were roused supports in this electrolytic solution of part immersion of said ribbon with the tight mode that contacts; The guard block that forms by non-conducting material; The part that does not closely contact with said ribbon of the lateral ends of the said ribbon that said guard block imbrication is supported with the mode of tight contact by said power supply drum and said power supply drum is with said end and the bulging influence that does not receive said electrolytic solution with those parts that said ribbon closely contacts of said power supply of protecting said ribbon; And driving part, this driving part makes said guard block and the said ribbon that closely contact with said power supply drum move in said electrolytic solution with the mode with the synchronization of said power supply drum.Therefore, can prevent fully to form the anodic oxidation overlay film, and can on the single surface of said ribbon, form the anodic oxidation overlay film through stable contact resistance in a side with the tight said ribbon that contacts of said power supply drum.
In addition, said ribbon is supported by the mode of said power supply drum with tight contact, makes it possible to direct back surface power supply from said ribbon.Therefore, can voltage be descended and inhibition to the negligible level of generating heat, thereby make it possible to increase LV.For this reason, even the resistance of the length of the per unit width of ribbon is higher, also can be to form the anodic oxidation overlay film at a high speed.
And, can in said power supply drum, recess be set, said ribbon contacts said recess and in said recess, moves, and perhaps guide reel can be set, and this guide reel is used for said guard block is expressed to said power supply drum.In these cases, improved the water resistance with the lower section, that is: horizontal said end and the bulging said ribbon of said power supply in the edge of the said ribbon of said guard block imbrication do not rouse the said part that closely contacts with this power supply.Therefore, can pass through more stable contact resistance forms the anodic oxidation overlay film on the single surface of said ribbon.
In addition, continuous anodic oxidation device of the present invention is the anodic oxidation device a plurality of of the present invention of arranged in series.Therefore, make it possible under the peaked situation that anodization fails can not take place in the power supply drum that surface current density is remained at each anodic oxidation device, make with LV N (N is the quantity of anodic oxidation device).As a result, can be formed on the AAO film that will have at a high speed the above thickness of 5 μ m and have on the high-resistance thin aluminium strip or on the ribbon of the composite conducting tinsel that has aluminium at least one surface.
Description of drawings
Fig. 1 is the schematic perspective view that anodic oxidation device according to an embodiment of the present invention is shown.
Fig. 2 is the schematic sectional view of the anodic oxidation device of Fig. 1.
Fig. 3 has to contact with ribbon and the front schematic view of the power supply drum of the recess of this ribbon move inside.
Fig. 4 illustrates power supply drum, ribbon and the width of guard block and the synoptic diagram of the relation between the diameter.
Fig. 5 is the schematic sectional view that illustrates according to the anodic oxidation device that is equipped with guide reel of another embodiment of the present invention.
Fig. 6 is the front schematic view that the power supply drum of the guide reel that is provided with Fig. 5 is shown.
Fig. 7 illustrates the schematic perspective view of the electromotive force of opposite electrode being arranged to the anodic oxidation device of negative polarity with respect to ground.
Fig. 8 illustrates a plurality of anodic oxidation device of the present invention by the continuous anodic oxidation schematic representation of apparatus of arranged in series.
Fig. 9 is the graphic representation that the relation between gait of march and the AAO system film speed is shown.
Embodiment
Hereinafter, will carry out detailed description to anodic oxidation device of the present invention with reference to accompanying drawing.Fig. 1 is the schematic perspective view that anodic oxidation device 10 according to an embodiment of the present invention is shown.Fig. 2 is the schematic sectional view of the anodic oxidation device 10 of Fig. 1.As depicted in figs. 1 and 2; Anodic oxidation device 10 of the present invention comprises: power supply drum 2; The mode with tight contact of being used for this power supply drum support by can anodised metal ribbon 1 or by at least one surface, have can anodised metal the ribbon 1 processed of composite conducting tinsel (below; Also abbreviate " ribbon 1 " as), what power supply was roused is made up of electro-conductive material with the part 2a that ribbon 1 closely contacts at least; Opposite electrode 3, said opposite electrode are arranged in the face of power supply drum 2 (in Fig. 1, omitted opposite electrode 3, understood other parts to be convenient to vision); Electrolyzer 5, this electrolyzer is filled with electrolytic solution 4, and the part that the mode with tight contact of opposite electrode 3 and power supply drum 2 supports ribbon 1 is immersed in this electrolytic solution; And the guard block 6 that forms by non-conducting material; The part 2b that closely contact with ribbon 1 of the lateral ends of the ribbon 1 that this guard block imbrication is supported with the mode of tight contact by power supply drum 2 and power supply drum 2 does not receive the influence of electrolytic solution 4 to protect the said horizontal end and the part 2b of the drum 2 of supplying power.
And; Provided upstream at power supply drum 2 is equipped with the donor rollers 21 that is used to supply with ribbon 1, and is provided with the winding roller 22 that is used to batch the ribbon of seeing off from power supply drum 21 (having carried out anodize on the surface at ribbon 1) in the downstream of power supply drum 2.In addition, between feed rolls 21 and power supply drum 2, be provided with the donor rollers 23 that is used to supply with guard block 6, and between power supply drum 2 and winding roller 22, be provided with the winding roller 24 that is used to batch guard block 6.Donor rollers 23 and winding roller 24 are arranged on the both sides of ribbon 1 so that guard block 6 imbrication ribbons 1 with not with the ribbon 1 tight part 2b that contacts.In winding roller 22 and 24, be provided with the driving part (not shown), and these driving parts are configured to make guard block 6 and the ribbons 1 that closely contacts with power supply drum 2 with mobile with the mode of the synchronization of power supply drum 2.
Note, described such situation here, wherein, be arranged in winding roller 22 and 24 each winding roller 22 of drive section drives with 24 to batch guard block 6 and to have carried out anodize ribbon 1 afterwards.Alternatively, winding roller 22 and 24 can be configured to freely to rotate and only be used to see off ribbon 1 and guard block 6, and the winding roller by isolating driving part control can be set in the more downstream of winding roller 22 and 24.Adopting under the situation of this structure, can winding roller 22 with by other winding roller that separates drive section drives between water rinse bath that is provided for anode purge oxidation ribbon and the dry slot that is used for the ribbon of dry water after cleaning.
The diameter of power supply drum 2 depends on that industrial scale and anode oxide film form speed, but in the scope of 50cm to 500cm, selects rightly usually.The part 2a with ribbon 1 closely contacts of power supply drum 2 is made up of electro-conductive material.The width of this electro-conductive material needn't be identical with the width of ribbon 1, and can be to allow the ribbon 1 tortuous width that moves.The width of this electro-conductive material preferably is positioned at 50% to 100% scope of the width of ribbon 1, and more preferably is positioned at 70% to 90% scope of the width of ribbon 1.
In anodic oxidation, surface current density is generally 500mA/cm
2Below.Therefore, the electric conductivity of the current-carrying part of power supply drum needn't be greater than 500mA/cm
2In addition, be under the situation of metal at the electro-conductive material of power supply drum, there is anode oxide film that the mist of contact resistance reason electrolytic solution forms and the possibility that changes along with the time.Therefore, preferably, the current-carrying part of this power supply drum is conductive plastics or conductive rubber.The soft surface of these materials, thus the use of these materials also prevent to damage aspect ribbon not anodized surperficial effective.Can utilize mixed carbon with the gp material of giving electroconductibility as conductive plastics or conductive rubber.The thickness of conductive plastics or conductive rubber will be according to hoping that intensity is with conductive characteristic and different.Yet preferably, the thickness of conductive plastics or conductive rubber is in the scope of 0.1mm to 10mm.Not not constituting by non-conducting material of power supply drum 2 with the part 2b that ribbon 1 closely contacts.Preferably with non-conductive plastics, non-conductive rubber etc. as non-conducting material.
Preferably, guard block is formed by non-conductive rubber, or the tinsel that is covered by non-conductive rubber.Can with the coated materials with adhesion characteristics guard block on the surface of tight contact ribbon 1 one sides.
Although this depends on the diameter of power supply drum, preferably, the guard block that Xiang Suiqi moves together applies tension force, so that guarantee water resistance.Under the bigger situation of the diameter of power supply drum, can advantageously utilize non-conductive string rubber as guard block with steel core.
Said ribbon by can anodised metal or at least one surface, have can anodised metal the composite conducting tinsel form.Can comprise by anodised metal: aluminium, Nb, Ta and Ti.This metal can be an alloy.For example, except fine aluminium, can also utilize duraluminum.Can advantageously adopt duraluminum with the purity more than 90%.Under the situation of utilizing the anodic oxidation overlay film as insulation layer, preferably, ribbon does not comprise as sedimentary metal Si particle.
Comprise with the example of the anodised melts combine of ability: iron with the metal of formation composite conducting tinsel; Carbon steel; Stainless steel; And Ti.The thickness of ribbon is usually in the scope of 0.02mm to 0.5mm.Because ribbon is supported to the drum of supplying power and closely contact, thus even the length of ribbon per unit width has high resistance, also can be forming at a high speed the anodic oxidation overlay film, thus can be directly from back surperficial power supply of ribbon.
The example of electrolytic solution comprises: acid, such as sulfuric acid, phosphoric acid, chromic acid, oxalic acid, tartrate, propanedioic acid, sulfonic acid, Phenylsulfonic acid and thionamic acid; The salts solution of acid; And composition thereof.Can select best electrolytic solution, so that obtain the quality of hope.The concentration of electrolytic solution and temperature can also suitably be selected.
Anodic oxidation device of the present invention makes ribbon 1 and guard block 6 move in electrolytic solution with the mode with the synchronization of power supply drum 2; Said ribbon 1 closely contact with power supply drum 2, said guard block 6 imbrication ribbons 1 along its horizontal end and not with the ribbon 1 tight part 2b that contacts.Therefore, can under the situation that does not adopt mask, prevent electrolytic solution 4 seepages, and this mask is essential conventionally on the single surface that the anodic oxidation overlay film is formed on ribbon the time.In addition, because ribbon 1 along its horizontal edge section fully by guard block 6 protection.Therefore, even, the side reaction that causes because of the local element reaction can not occur for having at joint such as carrying out anodised situation on the ribbon of the dissimilar metals of coating material yet.Because can prevent fully to form the anodic oxidation overlay film, so can on the single surface of ribbon, form the anodic oxidation overlay film at high speed through stable contact resistance in the side with the power supply drum closely contacts of ribbon.
In anodic oxidation device of the present invention; The confession ribbon 1 of power supply drum 2 and guard block 6 can form lessly along the diameter of its part that moves; Complications with the guard block 6 that suppresses imbrication ribbon 1 move, so that further improve the water resistance of the guard block 6 of imbrication ribbon 1.To describe this structure with reference to Fig. 3 and Fig. 4.Fig. 3 has the front schematic view that ribbon contacts with it with guard block and the power supply of the recess of move inside is roused.Fig. 4 is diagram power supply drum, ribbon and the width of guard block and the synoptic diagram of the relation between the diameter.It should be noted that in Fig. 3 and Fig. 4 the element that is equal to the element shown in Fig. 1 and Fig. 2 is marked by identical Reference numeral, and under situation about not needing especially, will omit its detailed description (this is applied to other figure equally).
Like Fig. 3 and shown in Figure 4, be provided with in power supply that the recess (notch) that supplies ribbon 1 contact and move inside contacts with confession guard block 6 and the recess of move inside in the drum 2.In Fig. 4, W
3And D
3Width and the diameter of representing power supply drum 2 respectively, W
2And D
2The width and the diameter in the outside of the part of the contact protection parts 6 of expression power supply drum 2 respectively, and W
1And D
1Represent the width of ribbon 1 and the diameter of the part that contacts ribbon 1 of power supply drum 2 respectively.Through setting the relation between the diameter of drum for D
3>D
2>D
1, and move by being arranged on the complications that recess in the power supply drum suppresses the guard block 6 of imbrication ribbon 1.Through setting the relation between the above-mentioned width for W
3>W
2>W
1, and make ribbon 1 by guard block 6 with high water resistance imbrication.Thus, can prevent more effectively that electrolytic solution from getting into the back surface of ribbon 1.Here, it should be noted that and described the recess that wherein supplies ribbon 1 contact and move inside and supplied guard block 6 to contact and the recess of move inside is arranged on the situation in the drum 2 of supplying power.Alternatively, can in power supply drum 2, only recess be set, ribbon 1 this recess of contact and mobile in this recess.
Anodic oxidation device of the present invention can be provided with guide reel, and these guide reels are pressed against guard block 6 on the power supply drum 2.To describe this structure with reference to Fig. 5 and Fig. 6.Fig. 5 is the schematic sectional view that illustrates according to the anodic oxidation device that is equipped with guide reel of another embodiment of the present invention.Fig. 6 is the front schematic view that the power supply drum of the guide reel that is provided with Fig. 5 is shown.Like Fig. 5 and shown in Figure 6, anodic oxidation device is provided with four guide reels 7 that are used to push guard block 6, wherein guard block 6 imbrication ribbons 1 along its horizontal end and the part 2b that does not closely contact with ribbon 1.The surface that it should be noted that these guide reels is insulated processing.Through guide reel 7 is set, ribbon 1 can be by guard block 6 imbrication under the situation that water resistance improves, thereby can prevent that electrolytic solution from getting into the back surface of ribbon 1 (surface that closely contacts with the power supply drum).
Here, it should be noted that the situation that shows the part place in the immersion electrolytic solution 4 that guide reel 7 wherein only is arranged on power supply drum 2.Alternatively, guide reel 7 can also be arranged on the part place in the electrolytic solution 4 of not immersing of power supply drum 2.For example, even guide reel 7 only is arranged on the part place (position between position between donor rollers 23 and the electrolytic solution 4 and winding roller 24 and the electrolytic solution 4) in the electrolytic solution 4 of not immersing of power supply drum 2, can prevent that also the complications of guard block 6 from moving.Therefore, guard block 6 can with the water resistance imbrication ribbon 1 that improves with not with the ribbon 1 tight part 2b that contacts.
In anodic oxidation, during reaction produce a large amount of hydrogen, and a large amount of hydrogen floats upwards and arrives the anodised surface of wanting of ribbon from opposite electrode.If, then will produce the anodic oxidation defective wanting to generate gaseous film on the anodised surface, thus, the essential electrolytic solution that stirs in the electrolyzer.Preferably, a plurality of holes are set in opposite electrode, to improve the efficient that stirs.The shape in these holes is according to alr mode and difference (in packaged unit, can use whisking appliance carry out stirring, and in large-scale plant, can in electrolytic solution, produce mobile).Yet the shape in these holes can suitably be selected among circle, Polygons, slit or mesh.The size in hole is according to the distance between power supply drum and the opposite electrode and different.Yet, from being applied to, uniform electric field wants anodized lip-deep viewpoint, and hole dimension excessively very much not is preferred.For example, the distance between power supply drum and opposite electrode is under the situation of 10cm, and preferably, the diameter of circular hole is below the 2cm.It should be noted that and to utilize the general use electrode that forms by carbon, aluminium etc. as opposite electrode.
During anodic oxidation, adopt direct current usually as power supply wave shape.Yet the optimum waveform of the AC wave shape that can select to overlap each other such as dc waveform is with the quality that obtains to hope.Current density during the anodic oxidation can freely be selected.For example, current density can be steady state value during whole anodize, perhaps during anodize, is increased.The electrolysis process that during anodic oxidation, adopts can be constant current process or constant voltage method.
Anodic oxidation forms the anodizing overlay film through supposition with respect to the electromotive force that opposite electrode has straight polarity.Preferably apply voltage, so that its electromotive force has negative polarity with respect to ground to opposite electrode.Through adopting this structure, can set the electromotive force of ribbon for closely electromotive force, and can the electromotive force with the entire equipment of roll-to-roll manipulation ribbon be arranged to earth potential.Under reverse situation, must give entire equipment with respect to the electromotive force on ground.This is not only dangerous, but also has the possibility that between ribbon and equipment, occurs such as the paradoxical discharge of spark, thereby causes the defective in the finished product.
Particularly preferably be, the electromotive force of ribbon is identical with ground, and the straight polarity output and the negative polarity output of electrolysis power are insulated with respect to ground.Through adopting this structure, the roll-to-roll part place except electrolyzer can prevent the paradoxical discharge between ribbon and the equipment fully.Fig. 7 schematically shows this structure.Through at least one conductive rollers 30 being set, can the electromotive force of ribbon 1 be arranged to earth potential, and roller 30 is electrically connected to ground at the roll-to-roll part place except electrolyzer 5.
And, preferably, be under the situation of constant current process or constant voltage method at electrolysis process (, electric current being flowed between power supply drum and opposite electrode) through this method, keep watch on the voltage with respect to ground potential of power supply drum.Through adopting this structure, can keep watch on the reason along the quality change longitudinally of ribbon of anodic oxidation overlay film, produce leakage current such as variation because of the contact resistance between the interim deterioration of the water resistance of guard block and ribbon and the power supply drum.
Preferably, opposite electrode 3 by across its in the face of with immerse electrolytic solution in the whole surface of the ribbons 1 that closely contacts of power supply drum 2 with about equally interval setting.Preferably, the shape of opposite electrode 3 is and power supply drum 2 concentric twisted plates.Yet; If opposite electrode 3 is equal fully apart from power supply drum 2 in electrolytic solution; Then will produce because of electric field at the part place of the entering electrolytic solution 4 of wanting anodised ribbon and the part place of leaving electrolytic solution 4 and concentrate the current concentration that causes, this possibly cause anodization fails.Therefore, preferably, effective electric field is less.The resistance that utilizes electrolytic solution is the simple method that is used to reduce effective electric field; And can opposite electrode be arranged to, make that the distance between opposite electrode and the power supply drum is bigger at the part place of leaving electrolytic solution of the part of the entering electrolytic solution of ribbon and/or this ribbon.Alternatively, can opposite electrode be arranged to, make not part and/or the part place of leaving electrolytic solution of this ribbon that opposite electrode is arranged on the entering electrolytic solution of ribbon.
Fig. 2 shows the layout of opposite electrode, and wherein, the distance between power supply drum 2 and the opposite electrode 3 is bigger at the part place of leaving electrolytic solution of the part of the entering electrolytic solution of ribbon and/or this ribbon.That is, get into the part place power supply drum 2 of electrolytic solution 4 and the distance P between the opposite electrode 3 at ribbon 1 by 2 supportings of power supply drum
1And leave the part place power supply drum 2 of electrolytic solution 4 and the distance P between the opposite electrode 3 at ribbon 1
2Be arranged to greater than the distance P between power supply drum 2 of the central part office in the immersion electrolytic solution 4 of ribbon 1 and the opposite electrode 3
3Here, distance P
1To P
3It is the shortest distance between power supply drum and the opposite electrode.Through opposite electrode is set in such a way, can reduce effective electric field, and can suppress to occur the anodic oxidation defective.It should be noted that Fig. 5 shows the layout that opposite electrode is not set at the part place that ribbon got into and left electrolytic solution.
Ribbon stands the clean as the preliminary step of anodize usually.This clean is from the surface removal pollutent of aluminium.For simplicity, adopt a kind of like this currently known methods, that is, such as ribbon is immersed in the alkaline solution, this alkaline solution works to dissolve neutral anodic oxidation overlay film and to remove pollutent.When needed, can also implement surface coarsening handles.This surface coarsening is handled protuberance and recess is set on the surface of anodic oxidation overlay film, to improve positive oxidation overlay film and the tight contact performance that forms another layer above that.Handle as surface coarsening, can adopt currently known methods such as mechanical surface roughening treatment, chemical surface method of roughening, electrochemical surface method of roughening and combination thereof.Anodic oxidation device of the present invention can be provided with the water rinse bath that is used to implement the preparation working groove of this preparation procedure of processing and is used for cleaning and removing from the upper reaches of donor rollers 21 Working liquids.
Simultaneously, the ribbon that after anodize, forms the AAO film stands drying treatment usually after passing the water rinse bath that cleans and remove electrolytic solution.
Next, the operation that sees figures.1.and.2 to anodic oxidation device of the present invention is described.At first, the ribbon 1 that twines around donor rollers 21 is rolled out and is supported by the mode of power supply drum with tight contact, then twines around winding roller 22.Similarly be that the guard block 6 that twines around donor rollers 23 is rolled out and twines around winding roller 24.At this moment, make the part 2b that does not closely contact with ribbon 1 of lateral ends and the power supply drum 2 of the ribbon 1 that guard block 6 imbrication are supported with the mode of tight contact by power supply drum 2, so that prevent the back surface of electrolytic solution entering ribbon 1.After realizing this state, in the electrolytic solution 4 in a part (for example, down to the center of rousing) the immersion electrolyzer 5 of power supply drum 2.Then, driving said driving part makes guard block 6 and the ribbons 1 that closely contacts with power supply drum 2 with mobile in electrolytic solution 4 with the mode of the synchronization of power supply drum 2.When connecting the power supply of anodic oxidation device 1, electric current flows between power supply drum 2 and opposite electrode 3, thereby with on the power supply drum 2 tight surfaces that contact does not form anode oxide film at ribbon 1.
Continuous anodic oxidation device shown in Figure 8 has the structure of arranged in series three anodic oxidation device 10a, 10b and 10c.This continuous anodic oxidation device is arranged to, and makes ribbon 1 supply with from donor rollers 21, transmits through anodic oxidation device 10a, 10b and 10c, then batches by winding roller 22 via transfer roller 25a, 26a, 25b, 26b, 25c and 26c.Guard block 6 is supplied with from donor rollers 23, transmits through anodic oxidation device 10a, 10b and 10c, then batches by winding roller 24 via transfer roller 27a, 28a, 27b, 28b, 27c and 28c.
Between donor rollers 21 and transfer roller 25a, be provided with the preliminary treatment groove 11 that is used on ribbon 1, implementing preliminary treatment.Be provided with the water rinse bath 12 and the dry slot 13 that is used for dry this ribbon after cleaning ribbon 1 that is used to utilize water anode purge oxidation ribbon between transfer roller 26c and the winding roller 22.It should be noted that in continuous anodic oxidation device shown in Figure 8, anodic oxidation device 10a, 10b and the 10c of arranged in series use guard block 6 jointly.Alternatively, anodic oxidation device 10a, 10b and 10c all can be provided with isolating donor rollers 23 and winding roller 24.
Although electrolytic solution and electrolytic condition are depended in anodizing of aluminium, the coulombic efficiency of electrolytic oxidation is approximately 3C/ (cm
2μ m), and system film speed have 100mA/cm
2The situation of electric current of surface current density under be approximately 2 μ m/min.At this moment, if this surface current density is designated as D1 (mA/cm
2), electrolysis time is appointed as T (min), and the essential thickness of AAO film is appointed as H (μ m), then T=50 * H/D1 (min).In addition, be designated as S if make film speed, then S=0.02 * D1, T=H/S thus.If the length of the ribbon in the immersion electrolytic solution is designated as L (m), and the gait of march of ribbon is designated as LS (m/min), then LS=L/T=0.02 * L * D1/H=L * S/H.Gait of march LS and L and D1 or S are proportional, and are inversely proportional to H.
Fig. 9 shows the graphic representation of the relation between the gait of march and AAO system film speed under the situation of 10 μ m of setting at the thickness H with the AAO film.The (a) and (b) of Fig. 9 and (c) represent that respectively the length L of electrolyzer wherein is respectively the situation of 5m, 10m and 15m.Gait of march LS can make film speed S with AAO to be increased pro rata.Under situation of the present invention, the length L of electrolyzer is along the distance that immerses the power supply drum in the electrolytic solution.For example, if the diameter of power supply drum be 3m and should rouse and slightly be deeper than its center immersion, then can electrolyzer length be arranged to 5m.The AAO film only is formed on the single surface of ribbon, and another surface keeps metallicity.Therefore, can under situation, carry out anodic oxidation continuously through the drum power supply.Thereby if an arranged in series N electrolyzer, then gait of march can increase N doubly.(b) in the graphic representation of Fig. 9 and (c) show gait of march under the situation of two and three electrolyzers of arranged in series respectively.The vertical axis on right side that it should be noted that the graphic representation of Fig. 9 is illustrated in the complete immersion type electrolyzer that will describe after a while every 1cm width along the direct of travel mobile Faradaic current of ribbon.For situation of the present invention, this electric current flows not as that kind noted earlier, but direct back surface power supply from ribbon.
As previously mentioned, in complete submerged conventional electrolysis device, must make Faradaic current flow to electrolyzer from power pack along the gait of march of ribbon with ribbon.At this moment; If the width of every 1cm is designated as D2 (A/cm) along the direct of travel mobile Faradaic current of ribbon, the amount that then generates the required electric current of AAO that must thickness on the area of the ribbon of time per unit in immersing electrolyzer is D2=LS * H * [coulombic efficiency] * 100/60=5 * LS * H.In this formula, gait of march LS is represented as m/min, and the thickness H of AAO film is represented as μ m, and coulombic efficiency is 3C/ (cm
2μ m).Thereby D2 is the proportional electric current of thickness with gait of march and AAO film, and does not depend on AAO system film speed or electrolyzer length.Represented value is used for wherein that the thickness of AAO film is the situation of 10 μ m on the vertical axis on the right side of the graphic representation of Fig. 9.Therefore, with respect to the vertical axis LS in the left side of this graphic representation, D2=50 * LS.
Simultaneously, exist to the upper limit that can flow to the electric current of electrolyzer from the power pack of ribbon.Thickness at aluminium foil is under the situation of 100 μ m, if increase the danger that fusing occurs through the IR heating (it produces heat dissipation) that the resistance of aluminium causes because electric current exceeds 150A/cm.Therefore, the Faradaic current of broad ways must be for below the 150A/cm, that is, gait of march must be for below the 3m/min, and irrelevant with system film speed or electrolyzer length during the electrolysis in the graphic representation of Fig. 9.The IR heat of ribbon generates the restriction electric current and is confirmed by the per unit resistance across sectional area with fusing restriction electric current.Therefore, this restriction electric current becomes littler along with the aluminium foil attenuation.In addition; This restriction electric current is also less for compound coating material; In this compound coating material, have HS and high-resistance metal (such as steel, stainless steel and Ti) and combine, and gait of march must reduce equally for these materials with aluminium.
It should be noted that in principle, can also improve LV through electrolyzer (ribbon immerses wherein fully) as a plurality of sections a plurality of routines that are installed in series.Yet this structure is unpractical, removes step and also becomes very necessary because only be formed under the single lip-deep situation mask adhering step and mask at the AAO film.In addition, adopting under the situation of supplying power indirectly in the immersion type electrolyzer fully, the power supply groove is set, and applies the voltage that has with anodised polar phase reversed polarity as method of supplying power to.Therefore, if a plurality of electrolyzers are set and carry out power supply indirectly, then during the power supply step, inverted voltage is applied to the AAO film of in preceding section apparatus, making, thereby produces such as the abnormality of separating the AAO film with multistage.Be formed at the AAO film under two lip-deep situation of ribbon, do not need mask.Yet the AAO overlay film is an insulating.Therefore, if the AAO overlay film is formed on two surfaces of ribbon, then multistage power supply is not only impossible, and according to aforementioned calculating, and wherein the AAO overlay film is formed on single lip-deep situation and compares, and need follow the into Faradaic current of direction mobile twice.Thereby the increase gait of march becomes even is more difficult.For this reason, continuous anodic oxidation device of the present invention will be formed on thin aluminium foil or have the single lip-deep situation of high-resistance coating material for the AAO film that wherein has the above thickness of 1 μ m, is a kind of extremely effectively structure.
Claims (12)
1. an anodic oxidation device is characterized in that, this anodic oxidation device comprises:
The power supply drum; The mode with tight contact of being used for this power supply drum support by can anodised metal ribbon or by at least one surface, have can anodised metal the ribbon processed of composite conducting tinsel, the constituting by electro-conductive material with the part that said ribbon closely contacts at least of said power supply drum;
Be arranged to opposite electrode in the face of said power supply drum;
Electrolyzer, this electrolyzer is filled with electrolytic solution, and what said opposite electrode and said power supply were roused supports in this electrolytic solution of part immersion of said ribbon with the tight mode that contacts;
The guard block that forms by non-conducting material; The part that does not closely contact with said ribbon of the lateral ends of the said ribbon that said guard block imbrication is supported with the mode of tight contact by said power supply drum and said power supply drum is with said end and the bulging influence that does not receive said electrolytic solution with those parts that said ribbon closely contacts of said power supply of protecting said ribbon; And
Driving part, this driving part make said guard block and the said ribbon that closely contact with said power supply drum move in said electrolytic solution with the mode with the synchronization of said power supply drum.
2. anodic oxidation device according to claim 1 is characterized in that:
In said power supply drum, be provided with recess, said ribbon contacts said recess and in said recess, moves.
3. anodic oxidation device according to claim 1 and 2 is characterized in that, this anodic oxidation device also comprises:
Guide reel, this guide reel are used for said guard block is squeezed in said power supply drum.
4. according to each the described anodic oxidation device in the claim 1 to 3, it is characterized in that:
In said opposite electrode, be provided with a plurality of holes.
5. according to each the described anodic oxidation device in the claim 1 to 4, it is characterized in that:
Stating the distance between power supply drum and the said opposite electrode by the part of the said electrolytic solution of entering of the said ribbon of said power supply drum supporting and/or the part place of leaving said electrolytic solution of said ribbon, stating the distance between power supply drum and the said opposite electrode greater than middle body place at the said electrolytic solution of immersion of said ribbon.
6. according to each the described anodic oxidation device in the claim 1 to 5, it is characterized in that:
Said guard block is non-conductive rubber or the tinsel that covered by non-conductive rubber.
7. according to each the described anodic oxidation device in the claim 1 to 6, it is characterized in that:
The electro-conductive material of said power supply drum is conductive plastics or conductive rubber.
8. according to each the described anodic oxidation device in the claim 1 to 7, it is characterized in that:
The electromotive force of said opposite electrode is a negative polarity with respect to ground.
9. according to each the described anodic oxidation device in the claim 1 to 8, it is characterized in that:
The electromotive force of said ribbon is identical with earth potential, and the output of electrolysis power is insulated with respect to ground.
10. according to Claim 8 or 9 described anodic oxidation devices, it is characterized in that this anodic oxidation device also comprises:
Supervision portion, this supervision portion are used to keep watch on the voltage with respect to earth potential of said power supply drum.
11. a continuous anodic oxidation device is characterized in that, this continuous anodic oxidation device comprises:
Arranged in series a plurality of according to each the described anodic oxidation device in the claim 1 to 10.
12. a film-forming method is characterized in that:
Employing comes on the surface of ribbon, to form the anodic oxidation overlay film according to each described anodic oxidation device in the claim 1 to 10 or continuous anodic oxidation device according to claim 11.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-089983 | 2010-04-09 | ||
| JP2010089983 | 2010-04-09 | ||
| JP2010162693A JP4723041B1 (en) | 2010-04-09 | 2010-07-20 | Anodizing equipment |
| JP2010-162693 | 2010-07-20 | ||
| PCT/JP2011/002088 WO2011125336A1 (en) | 2010-04-09 | 2011-04-08 | Anodic oxidation device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102834550A true CN102834550A (en) | 2012-12-19 |
| CN102834550B CN102834550B (en) | 2015-05-06 |
Family
ID=44350518
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180018267.8A Expired - Fee Related CN102834550B (en) | 2010-04-09 | 2011-04-08 | Anodic oxidation device |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20130026045A1 (en) |
| JP (1) | JP4723041B1 (en) |
| CN (1) | CN102834550B (en) |
| WO (1) | WO2011125336A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105980610A (en) * | 2014-02-05 | 2016-09-28 | 蒂森克虏伯钢铁欧洲股份公司 | Component oxidized by plasma electrolysis and method for the production thereof |
| CN111793816A (en) * | 2020-07-31 | 2020-10-20 | 常州费曼生物科技有限公司 | Continuous anodizing equipment and process for single-side anodizing porous infusion apparatus filter membrane |
| CN112813477A (en) * | 2020-12-24 | 2021-05-18 | 西比里电机技术(苏州)有限公司 | Method and equipment for moving workpiece type thermoelectric chemical oxidation |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608492A (en) * | 2011-06-14 | 2014-02-26 | 富士胶片株式会社 | Anodizing device, continuous anodizing device, and film forming method |
| CA2995815C (en) * | 2015-06-22 | 2021-08-24 | The Brigham And Women's Hospital, Inc | Home evaluation of the quality of semen samples |
| CN108839352B (en) * | 2018-07-03 | 2023-10-03 | 华玻视讯(珠海)科技有限公司 | Multistage film laminating machine for protecting IR holes of display glass screen |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20130026045A1 (en) | 2013-01-31 |
| JP4723041B1 (en) | 2011-07-13 |
| WO2011125336A1 (en) | 2011-10-13 |
| CN102834550B (en) | 2015-05-06 |
| JP2011231395A (en) | 2011-11-17 |
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